Yarn conditioning process and composition therefor



Patented Sept. 16, 1941 UNITED STATES arson:

YARN CONDITIONING PROCESS AND COM- POSITION THEREFOR Joseph a. money. Eastman Kodak Rochester, N. Y Com corporation of New Jersey .No Drawing. Application September 18, 1940,

Serial No.

15 Claims. (Cl. 28-1) This invention relates to the treatment of cellulose organic derivative filaments, fibers, threads and the like and more particularly to a method of eliminating the tendency of such materials to accumulate charges of static electricity tion also relates particularly cellulose organic derivative cut staple fibers to adapt them for the manufacture of spun yarns.

As is well-known, cellulose organic derivative materials, particularly in filament, yarn, or sheet form, are particularly subject to the accumulation on their surfaces of charges of static electricity from frictional and other influences. In the case of filaments and yarns in which the surface area of the material (per unit of weight) is enormously greater as compared to sheets or films, the problem of static often assumes serious proportions. In the manufacture of yarns of various types from artificial filaments, numerous steps in which the yarn is subjected to frictional influences may be necessary, as for example, twisting, winding, warping, carding, combing, drawing, spinning and the like, all of which operations tend to produce large accumulations of static on the filaments' aggravated in the utilization of cut staple, as for example, in the making of spun yarn, since in carding and combing considerable friction is developed and as a result sufilcient charges accumulate n the fibers to make the formation of the web difiicult, if not impossible; furthermore, even if a web is formed with some degree of success, the subsequent drafting operation produces a very uneven spun yarn or intermediate roving due to the presence of the static charge. In addition, there is the ever-present fire hazard.

Cellulose derivative yarn, particularly in the form of cut staple, is extremely difficult to handle in the various operations involved in making spun yarn, not only because such material is composed of filaments having smooth, glass-like surfaces without natural kink or irregularity, but also because it has relatively negligible moisture content at normal humidities, as compared to natural fibers such as cotton and wool, making it inherently far more susceptible to the accu mulation of static. The charges accumulating on cellulose derivative cut staple fibers are, under some circumstances, even sufficient to separate the individual fibers a distance of inches, notwithstanding their relatively minute size.

This invention has as its principal object to provid, an improved method for the treatment of cellulose organic derivative yarns to reduce or eliminate the tendency of such yarns to accumulate charges of electricity under frictional and other influences. A further object is to provide a method of facilitating the handling and employment of cellulose organic derivative cut 1 the manufacture of spun This is particularly assignor to Rochester, N- Y a staple fibers in the various operations involved in yarns. A still further object is to provide a method of treating cellulose organic derivative yarns in either filament or cut staple form, wherein the material is simultaneously softened and lubricated and the accumulation of static charges thereon'is prevented. Another object is to provide an improved type of cellulose organic derivative cut staple having little or no tendency toward accumulation of static electrical charges. .Other objects will appear hereinafter.

These objects are accomplished by the following invention which in its broader aspects comprises applying to cellulose organic derivative yarns either in the form or filaments, threads or staple fibers, an antistatic composition containing as its essential antistatic component a phosphonic acid of a ketone containing one or two naphthenyl groups or a salt thereof. We have found that compounds having the general formula:

wherein R. is a substituent selected from the group consisting of hydrogen, alml, alkylene,

OH nsphthsnyl naphthenyi wherein R has the meaning referred to above. If the reaction is stopped at the intermediate stage naphthenyl mixed acids can be formed by treating with a different aldehydic or ketonic compound. These mixed acids may be represented by the formula:

on on n- P v d-a' nsplithenyl wherein R has the meaning referred to above, R. and R. are similar to R and wherein R and R may be part of the same system of cyclic carbon atoms. Products of the type illustrated by this formula areobtained by reacting compounds of the type illustrated'by the structural formula with hypophosphorous acid and then with comer'al the products invention prepared pounds illustrated by the structural formula the technique described above,

. RI RI I '7 0E. I l o. 51 aha. wherein R and B have the meaning referred to above. Hf PREPARATION or Acme p naphtha, Intermediates required i'or the preparation of imam PM?! $911M?! hydro mdroxy the new phosphonic acids 01 ketonesoi our in- 10 Md) vention are described in the copending appli- 3 cation of J. B. Dickey and J. G.McNa11y Ser. No. B naphthenyl 5 p 320,718, filed February 24, 1940, in U. 5. Patents 1,988,021 and 1,989,325 and in Lewkowitsch,

"Chem. Technology of Oils, Fats, and Waxes," 15 wmphthwvlhvdrw phomcwd) 6th edition, 1, p. 146-155. By the term naphisopropyl' thenyl we refer to radicalsot the general class naphthenyl on described in chapter 48 of The Chemistry of C Petroleum Derivatives by Carleton Ellis. w mntrl Typical examples of the preparation or this v H 3 OH cm type of compound are given below: 80'}! Exam Ze1 (2-isopropyl-8-sulf 1- hthl hth p ydmtyl gha-cgclogifiyl :F ne 3133365111333? 3 moles of phenylnaphthenyl ketone are heated H H with 66 g. of hypophosphorus acid for one day or C=G more at a temperature of 60-100. Upon cooling 0 a product having the formula: D 0 [naphthenyITP/ a O--naphthenyl l 6H. \0H l fi H y n phthenylhydroxymethmphosphonicacid) r (bis-phenylnaphthenyl hydroxy methane phosphonic acid) 3 OH crystallizes out. There is also formed some y $-OOH on, OH I CHr-CH; I

t-r-(oml i I on naphthenyl 40 i n which is quickly oxidized to ,ti' drtiy tfittitififitfifiiflm OE l O-{J-naphthenyl HZNQOH r z: I l naphthenyl Example 2 l-' 2.5 gram moles methylnaphthenyl ketone are o reacted with 66 g. of hypophosphorus acid as in bi p Example 1. The product has the formula: s. ydmy 5.8mm; tiiifinififie t cm CH;

7 CH: H04!P 0-011 G NH. 0 0H naphthenyl I 0 naphthenyl 1 n n yl (bis-alpha-naphthenyl-alpha-hydroxy ethane phosphonic acid) 6=P0 Example 3 gggg f afigw y hydmxymethano One-gram mole of dinaphthenyl ketone is re- PREPARATION SALTS acted with 66 g. of hypophosphorus acid as in Example 1 and the intermediate product thus Emmi-7184 formed is heated as before with two moles of one mole Y methylamyl ketone. 'The product has the formula: 3 00001 1. (Naphthenyl) 0 on on naphthmyl stml H cm , H is treated in water with 1 mole potassium hy- 1 5 droxide. The product, potassium bis-naphthenj-naph eny hy y e g -h r y h p p p v yl acetoxy stearyl methane phosphonic acid salt, is slightly soluble in hot water. In place of The compounds listed below represent in gen- 7 potassium I may prepare the sodium, am-

cose, cotton,

monium, calcium, barium, magnesium, salts.

eta,

Example One mole of naphthenyl-(iJ-CH;

yl-amine, morpholine, ethylenediamine, tetramethylammonium hydroxide, etc.

In accordance with my invention, the abovementioned compounds may be applied to the yarn in any convenient manner, for example, by roll, wick, immersion, spraying or the like. In-

asmuch as these compounds are soluble in oil dispersed in oils such they may be dissolved or as mineral oil, blown and unblown, drying, and semi-drying, vegetable and animal oils, examples of which are light mineral, neat's-foot, olive, teaseed, castor, soya bean, rapeseed oils, etc., and other lubricants.

In the following examples and description, I have set forth several of the preferred embodiments of my invention, but they are included merely. for purposes 01 illustration and not as a limitation thereof.

Example 6 OH Naphthenyl-(J-OH:

O=1-0H Diethanolamlne salt (bis-alpha naphtheny -atlphs-hydroxy ethane phosphonic acid v d ie hauolamine salt) is applied to textile materials (silk, wool, viscellulose acetate) by means oi! a wick, bath, roller, spray, etc., to facilitate their knitting, weaving, spinning, and thelike. Yarns lubricated with the above types of lubricants are 5 suitable lubricating mixtures having antistatic properties which are used as illustrated in Examples 8 and 7 follow.

' Example 8 0H 0 10 i Parts bisolsylamine salt 1-10 O'E naphtlienyl OH I (bis-meta-sullohen 1 na hthen l h an methane hoe Shout acifbis-oieylam ine t) p Olive on os-oo Example 9 11-0 C-H/OE H! -C 0 naphthenyl ONa (bis-nsphthenyl iuryl hydroxy methane phosphonic acid sodium salt) Blown olive oil... 99-80 of special value in the preparation of cut'staple fibers. These fibers may be oiled before or after cutting.

Example 7 A conditioning liquid is made up as follows:

Parts Butyl naphthenate...-..'. 90-95 ECO-CH:

1- -c H Naphtheny. Diethylcyclohexylamine salt 10-5 CH; CH:

i ll tit'lhtiittifiitlhfilfitfifiiiitiit and applied to textile materials such as silk, wool, cotton, viscose, cellulose acetate, etc., as described in Example 6. If the yarn is intended primarily for knitting, the amount of conditioning liquid applied may vary from 2-25% by weight oi the yarn and if for weaving, between by weight.

Cellulose acetate above are quite soit and pliable and give improved results in textile operations such as weaving, knitting. etc., and especially in the preparation' oi! cut staple yarn. Other examplu o! Example 10 naphthenyl OC0C4H0 Parts \(g E-OH Butylamine salt-.. l-lO aphthenyl (bis-dinaphthenyl alplia-butoxy methane phosphoaic acid butylamine salt) Mineral oil- 99-00 Example 11 Butylstearate ll Mineral oil 39- 0 0 GET-CH, l i nsphthenyl- -C0E OH:

H H Gila-CH: 40

CH CH: Tributylamine salt 1-10 Ha i 7 C i (cyclohexyl naphthenyl-hydroxy methane-a1 ha-h dro oyclohexane phosphonicacidtributyl 811111 2988" y Example 12 on on naphthenyll-PJICH: .1. 313:

H: B'- i Di-beta-methoxyethylamine salt (alpha-11a hthenyl-alpha-hydroxy ethane-beta-hydroxy heptane p osphonic acid di-beta-methoxy ethyla'mine salt) Neats-loot oil- 90-10 Example 13 OH OH.Tetramethylammonlum hydroxide H Parts naphthenyl- -Cnaphtbenyl 1-10 H: H (bis-alpha-naphthenyl-alpha-h droxy ethane phosphonic acid tetramethyiammo umhydroxids salt) Blown neats-ioot 99-90 6 5 Example 14 Parts s nil 55 filaments treated as described (bis-dinaphthenyl hydroxy methane phosphonic acid tetrahydroiuriurylamine salt) Butyl naphthenst Mineral oil Example 15 Parts Blown sperm oil... a 68 V nephthenyl H H.Tri-betn-metho th 1- ine sal phenyi 0 i ht l hen I h dro methane hosphonic acid (b a nap iataiethzxy :Ewlamine salt) Water 2 10 Di-beta-metbolyethyl succinate 20 Example 16 2C1]; N\ v O CH: v 0H1 rims on c r-on l-lO I I C (11H: 0 20 H] v i ii] h -tetralin-l-dimeth lamino-fl-elpha-hydroethane phos- (bsl p a ph nic acid) Teaseed oil 99-90 Example 17 Parts Blown teaseed oil 38-20 (ll oeroiaoetone 50-70 y naphtbenyl\OH' i --lT-0H.Benzylamine salt 1-5 om-o-o1n i hebthen mete-memo euum phosphonic acid (bwp mp y] benzylamine salt) CH: -/0H H0J7P\ v 42E; 3 0H.Diethylcyclohexylamine salt 'i-t ta-h dro home acid diethylcyclohexyl- (B y ynmo u p p amt) Eel-ample 18 OH l l l(suli ted) Bis-cyclohexylamine PM t e one p y y Sm .45

0 in Y ise hthen l oieyl (sulionated) hydroxy methane phos- (b n p p onlc acid biscyclohexylamine salt) Blown olive on 30-40 Blown neets loot oil 69-50 Etamnle 19 Y Parts Olive oil -60 Suilonatedcastnr 10 55 Mineral oil 20 Oieic acid v 10-15 0 0H.sodium salt in 1 on on nap bony a 5 I O-phenyl 0 cyclohexyl methyl na hthenl clohe hydrory methane-methyl phony] p y h gdroxy r ethane phosphonic acid) Example 20 Parts Water 7o Watersolubleeelluloseester I l5 naphthenyl 0H 0H P- -CH; 5 H methyl ONa meth ln'a hthen lh dmxy methane-alpha-hydroxy ethane p p osphonioaddsodiumsalt) B ullonated olive oil 4 10 Example 21 v (IJHIJ: g and three pounds of sugar. The resulting finely divided mixture is then added to gallons water heated to 60-80 and the resulting aqueous suspension is used to dye about 100 pounds cellulose acetate.

Any of the above compositions may be applied to the yarn intended for use in circular knitting by means of a bath, wick, spray, roller, pad or any suitable means. The amount of conditioning liquid applied may vary between 545% by weight of the yarn. Usually, however, the amount of conditioning liquid applied is about Ill-45% by weight of the yarn. Yarn composed of celluloseacetate conditioned as described above gives excellent results when used in the circular knitting process.

If the conditioning agent is to be applied to the yarn after spinning, this may be done by bringing the yarn in contact with a wick,'roll, or felt wet therewith, or the liquid may be applied by immersion, spray, or otherwise. The

particular point at which the liquid is applied may vary. It may, for example, be applied to the yarn inside or outside the spinning cabinet, between the guide and godet roll, between the godet or other roll or guideand the point of winding and/or twisting. In some cases, the liquid may even be applied to the yarn after winding onto cones; spools, bobbins, or the like or by the socalled bobbin to bobbin" method. In the case of staple fiber manufacture, the liquid may be applied to the yarn prior 'to, or after cutting into staple lengths.

The amount of the agent so employed will vary widely depending upon the results desired, the specific nature of the material to which the agent is applied, the use to which the yarn is eventually to be put and other factors. For example, in a given case where a cellulose organic acid ester yarn such as a yarn composed of cellulose acetate is intended for knitting, about 4 to 25% or more by weight, based on the weight of the dry yarn, may be satisfactory, while if the yarn is intended for weaving, the amount may vary between about 1 and 5%.

Although in the above examples I have referred primarily to yarn treating compositions containing only the conditioning agent and an oil, other ingredients such as solvents, non-solvents, emulsifying agents, blending agents and the like. may be added within the scope of my invention. Likewise, various dyes or other coloring matter may be included in case nently or fugitively tint undergoing treatment.

Although I have found it convenient to illustrate my invention by reference to compositions containing specific percentages of the various ingredients, these percentages may vary widely depending upon the particular purpose for which the composition is intended. For example, if it or dye the material is desired to control the 'deelectrifying action of 4 amount of the agent the conditioning agent, the may be adjusted as, for example, by reducing the amount of the agent, an creasing the amount of oil or other ingredient.

While I have described my invention with parit is desired to permad correspondingly inticular reference to the treatment of yarns composed of organic derivatives cellulose acetate, the conditioning agents and formulas described herein are applicable to the conditioning of many other types of cellulose derivative yarns such as thosecomposed of or containing cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, ethyl cellulose, methyl cellulose, benzyl cellulose and others, as well as to the conditioning of silk, wool, cotton, viscose and other natural or artificial materials.

The term "yarn as used herein and in the claims is to be understood as including a single filament, a plurality of filaments associated into the form of a thread, either of high or low twist, single or multiple threads associated or twisted together, composite threads composed of a mixture of natural and artificial filaments or a composite thread formed by twisting together individual strands of natural or artificial materials, as well as cut staple fibers produced from natural and/or artificial filaments or threads and spun yarn produced from such staple fibers.

As indicated above, the yarn conditioning agents of my invention are exceptionally good solvents for a wide variety of mineral, blown and unblown, drying and semi-drying animal and vegetable oils such as cottonseed, olive, castor, neats-foot, sperm and other oils. This enables them to be used with any of such oils in making of cellulosesuch'asup a variety of yarn treating formulas of varying composition.

The yarn conditioning agents of my invention also have exceptional value as surface-active compounds and as such may be employed as wettin agents, emulsifying and dispersing agents, textile assistants, dye dispersing agents and the like.

The yarn conditioning method and compositions of my invention possess many outstanding advantages. The fundamental and outstanding characteristic of the agents employed in accordance with the invention is their ability to deelectrify yarns, especially those composed of or containing organic derivatives of cellulose such as cellulose acetate and render them amenable to various textile operations, especially operations such as those involved in the manufacture of cut staple fibers, as well as in weaving and knitting. Another outstanding characteristic of these compounds is their exceptional solvent power for a wide variety of mineral, animal, and vegetable oils and their ability to act as lubricating assistants in conjunction with these oils when applied to such yarns.

In addition, due to their solubility in water, they may be readily removed from yarns and fabrics by means of the usual aqueous scour baths.

Of the above compositions I have found that bisphenyl naphthenyl hydroxy methane phosphonic acid,bis-alpha-naphthenyl-alpha-hydroxy ethane phosphonic acid, and bis-naphthenyl hydroxy methane phosphonic acid are outstanding in their ability to reduce or eliminate the tendency of yarns composed of or containing organic derivatives of cellulose to accumulate charges of static electricity.

What I claim is:

l. The method of eliminating the tendency of yarns, filaments or fibers to accumulate charges of static electricity, which comprises applying thereto a composition-containing as its essential anti-static component a phosphonic acid of a ketone having the general formula:

- 1 OH on R;P;-+-R

O/AH naphthenyl naphthenyl wherein R is a substituent selected from the group consisting of hydrogen, alkyl, allrylene, aryl, heterocyclic, cycloalkyl and naphthenyl.

2. The method of eliminating the tendency of yarns, filaments or fibers composed of or containing organic derivatives of cellulose to accumulate charges of static electricity, which comprises applying thereto a composition containing as its essential anti-static component a phosphonic acid of a ketone having the general formula:

on on 11- -;r- +-a O/(BH naphthenyl naphthenyl wherein R is a substituent selected from the I group consisting of hydrogen, alkyl, allcylene, aryl, heterocyclic, cycloalkyl and naphthenyl.

3. The method of eliminating the tendency of yarns, filaments or fibers composed of or containing cellulose acetate to accumulate charges of static electricity, which comprises applying thereto a composition containing as its essential anti-static component a phosphonic acid of a ketone having the general formula:

on OK O H naphthenyl naphthenyl wherein R is; a substituent selected from the group consisting of hydrogen, alkyl, alkylene, aryl, heterocyclic, cycloalkyl and naphthenyl.

4. The method of eliminating the tendency of yarnsrfilaments or fibers composed of or containing organic derivatives of cellulose to accumulate charges of static electricity, which comprises applying thereto a composition containing as its essential anti-static component bisphenyl-naphthenyl hydroxy methane phosphonic acid.

5. The method of eliminating the tendency of yarns, filaments or fibers composed of or containing organic derivatives of cellulose to accumulate charges of static electricity, which comprises applying thereto a composition containing as its essential anti-static component bis-alphanaphthenyl-alpha-hydroxy ethane phosphonic acid.

6. The method of eliminating the tendency of yarns, filaments or fibers composed of or containing organic derivatives of cellulose to accumulate charges of static electricity, which comprisesapplying' thereto a composition containing as its essential anti-static component bis-naphthenyl hydroxy methane phosphonic acid.

'7. Textile yarns having a lessened tendency to accumulate charges of static electricity, said yarns containing a phosphonic acid of a ketone having the general formula:

group consisting of hydrogen, alkyl. alkylene, aryl, heterocyclic, cycloalkyl and naphthenyl.

8. Textile yarns composed of or containing organic derivatives of cellulose having a lessened tendency to accumulate charges of static electricity, said yarns containing a phosphonic acid oi a ketone having the general formula:

wherein R is a substituent selected from the group consisting of hydrogen, alkyl, alkylene,

aryl, heterocyclic, cycloalkyl and naphthenyl.

9. Textile yarns composed of or, containing cellulose acetate having a lessened tendency to accumulate charges oi. static electricity, said yarns containing a phosphonic acid oi a ketone having the general formula:

on on otn naphthonyl nap'hthcnyl wherein R is a substituent selected from the group consisting of hydrogen, alkyl, alkylene, aryl, heterocyclic, cycloalkyl and naphthenyl.

l0. Textile yarns composed 01' or containing cellulose acetate having a lessened tendency to accumulate charges oi. static electricity. said yarns containing a phosphonic acid oi. a ketone having the general tormula;

wherein R is a substituent selected from the group consisting of hydrogen, alkyl, alkylene,

aryl, heterocyclic, cycloalkyl and naphthenyl, and

a textile lubricant.

11. Textile yarns composed or or containing organic derivatives of wherein R is a substituent selected from the ygroup consisting of hydrogen, alkyl, alkylene,

aryl, heterocyclic, cycloalkyl andnaphthenyl. 15.- A textile yarn anti-static composition containing as its essential anti-static component a phosphonic acid having the formula:

OH on: OH 7 n- R naphthenyl where R, R and R are substituents selected from the group consisting of hydrogen, alkyl, alkylene, aryl, heterocyclic, cycloalkyl and naphthenyl groups and wherein R and 1? may be part oi the same system of cyclic carbon atoms.

JOSEPH B, DICKEY.

cellulose having a lessened tendency to accumulate charges of static elec- 

